Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
  • C03B37/01—Manufacture of glass fibres or filaments
  • C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
  • C03B37/025—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from reheated softened tubes, rods, fibres or filaments, e.g. drawing fibres from preforms
  • C03B37/028—Drawing fibre bundles, e.g. for making fibre bundles of multifibres, image fibres
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
  • C03B19/025—Other methods of shaping glass by casting molten glass, e.g. injection moulding by injection moulding, e.g. extrusion
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C13/00—Fibre or filament compositions
  • C03C13/04—Fibre optics, e.g. core and clad fibre compositions
  • C03C13/048—Silica-free oxide glass compositions
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/12—Silica-free oxide glass compositions
  • C03C3/16—Silica-free oxide glass compositions containing phosphorus
  • C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B2203/00—Fibre product details, e.g. structure, shape
  • C03B2203/40—Multifibres or fibre bundles, e.g. for making image fibres
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B2205/00—Fibre drawing or extruding details
  • C03B2205/56—Annealing or re-heating the drawn fibre prior to coating
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2213/00—Glass fibres or filaments
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
  • G02B6/02—Optical fibres with cladding with or without a coating
  • G02B6/02395—Glass optical fibre with a protective coating, e.g. two layer polymer coating deposited directly on a silica cladding surface during fibre manufacture
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
  • G02B6/04—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings formed by bundles of fibres

Definitions

• the disclosure relates to organic-inorganic composites, composite fibers, and to methods thereof.
• the disclosure provides organic-inorganic composites, composite fibers having micro- and nano-scale diameters, articles including the composite fibers, and to methods of making and using the composites and composite fibers.
• the disclosure provides an organic-inorganic composite having high optical transparency and comprising fibers or filaments of an inorganic material in an organic matrix such as in the form of a fiber, which organic matrix encapsulates the inorganic fibers or filaments.
• the disclosure provides an organic-inorganic composite having discontinuous inorganic domains substantially along two dimensions or two axes, for example, a fiber bundle, a honeycomb structure, a fiber, and like structures.
• the disclosed organic-inorganic composite has fibers or filaments of inorganic material that are elongated and have cross-sectional diameters, for example, less than about 10 microns, and an aspect ratio (i.e., length / diameter), for example, of from about 100: 1, of from about 1000:1 , or of from about 10,000: 1, including intermediate values and ranges.
• the disclosed organic-inorganic composite has a high optical transparency characterized by a total optical transmission (e.g., specular and diffuse) greater than about 20% when measured in the axial direction through a 1 mm cross-section of the fiber, or when measured in the axial or transverse direction through a cross-section of the fiber (or a bonded bundle of fibers) that is greater than about 100 microns in thickness.
• a total optical transmission e.g., specular and diffuse
• the disclosed organic-inorganic composite can have a discontinuous phase comprised of an inorganic material, and the inorganic material can be, for example, an oxide glass, a fluoride glass, or an oxyfluoride glass.
• the disclosed organic-inorganic composite can have an organic matrix that can be, for example, a thermoplastic polymer, for example, a polyetherimide (PE1), a polyethersulfone (PS), a polyimide, and like polymers, or mixtures thereof.
• a thermoplastic polymer for example, a polyetherimide (PE1), a polyethersulfone (PS), a polyimide, and like polymers, or mixtures thereof.
• the disclosure provides a method for making and using the disclosed composite(s).
• Fig. 1 shows images of process steps leading to a fiber draw step 1.
• Fig. 2 shows images of process steps leading to fiber draw step 2.
• Fig. 3 shows SEM cross-section images of fibers resulting from fiber draw step 3.
• Fig. 4 shows an SEM cross-section image of some of the smallest individual fiber/filaments within the composite matrix resulting from fiber draw step 3.
• the term "about” also encompasses amounts that differ due to aging of a composition or formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing a composition or formulation with a particular initial concentration or mixture.
• indefinite article “a” or “an” and its corresponding definite article “the” as used herein means at least one, or one or more, unless specified otherwise.
• compositions and methods of the disclosure can include any value or any combination of the values, specific values, more specific values, and preferred values described herein, including explicit or implicit intermediate values and ranges.
• the disclosure provides a method of improving the crack resistance of organic-inorganic composites, specifically, the crack resistance can be increased dramatically as the individual domain sizes are reduced below 1 micron, and especially when domain sizes are reduced into the 20 to 500 nm range (see e.g., Cordero, et. al., "Channel cracks in a hermetic coating consisting of organic and inorganic layers," Appl. Phys. Lett. 90, 111910 (2007)).
• crack growth can be arrested or deflected at domain interfaces, thus limiting the effective flaw size, stress intensity at crack tips, or both, leading to enhanced toughness.
• These materials are typically characterized by high inorganic content (e.g., greater than 80% by volume), 20 to 500 nm domain sizes, high adhesion between organic and inorganic phases, and high ductility of the organic phase.
• high inorganic content e.g., greater than 80% by volume
• 20 to 500 nm domain sizes high adhesion between organic and inorganic phases
• high ductility of the organic phase A few of these biological materials have been found to exhibit good optical transmission (see Li, et. al., supra.).
• These materials combine the strength from the inorganic phase with toughness produced by the nanostructure and ductile organic phase.
• Recently, some of these biological nanocomposites have been measured to have a tensile strength as high as 3 to 6 GPa, a tensile modulus of about 120 GPa, and a failure strain of 4 to 6% (see Barber, et. al., supra.).
• the disclosure provides an organic-inorganic composite, comprising:
• discontinuous phase comprised of a plurality of adjacent and similarly oriented (e.g., substantially parallel) fibers of an inorganic material
• thermoplastic polymer a continuous organic phase comprised of a thermoplastic polymer
• the continuous organic phase surrounds the plurality of adjacent and similarly oriented fibers of the inorganic material
• the organic -inorganic composite is a plurality of adjacent and similarly oriented fibers of inorganic material contained within or surrounded by a similarly oriented host fiber of the thermoplastic polymer.
• the inorganic material can be, for example, an oxide glass
• the organic phase can be, for example, a thermoplastic polymer.
• the oxide glass can be, for example, zinc sulfophosphate ("ZSP")
• the thermoplastic polymer can be, for example, selected from a polyetherimide (PE1), a polyethersulfone (PS), a polyimide, and like polymers, or mixtures thereof.
• the oxide glass can have, for example, a glass transition (Tg) temperature from 200 to 450°C, including intermediate values and ranges.
• Tg glass transition
• the oxide glass can have, for example, at least one characteristic average dimension of from 0.01 to 10 microns, such as 0.1 to 9.9 microns, 0.2 to 9 microns including intermediate values and ranges.
• the disclosure provides a method of making the above mentioned organic-inorganic composite, comprising: a first melting at a suitable temperature (e.g., at 800°C for 3 hrs in covered Pt crucible), a batch (or a plurality of batches) of suitable proportions of inorganic sources or precursors comprising:
• lithium phosphate 8 to 12 % lithium phosphate, or for example, a mixture of P 2 O 5 and Li 2 0;
• the method can further comprise, for example, a second melting (e.g., at 800°C for 3 hrs in covered Pt crucible) of the product of the first melting.
• a second melting e.g., at 800°C for 3 hrs in covered Pt crucible
• the second melting or “remelting” can be, for example, optional and is unnecessary if different melting equipment such as having greater batch capacity is available.
• the method can further comprise, for example, pouring or extruding the product of the first melt into a rod (e.g., 1x6 inch rods) and annealing the rod at (e.g., 320°C) to form an annealed ZSP glass rod.
• a rod e.g., 1x6 inch rods
• annealing the rod at e.g., 320°C
• the method can further comprise, for example, extruding the annealed ZSP glass rod form an extruded and annealed ZSP glass rod. (e.g., at from 400 to 600°C, or 450 to 550°C).
• the method can further comprise, for example, wrapping the extruded and annealed ZSP glass rod in a thermoplastic polymer film selected from a polyetherimide (PE1), a polyethersulfone (PS), and like polymers, or mixtures thereof, to form a polymer wrapped glass rod, with the thermoplastic polymer film having a thickness of from 0.1 to 5 mm as shown in Fig. 1.
• a thermoplastic polymer film selected from a polyetherimide (PE1), a polyethersulfone (PS), and like polymers, or mixtures thereof.
• the method can further comprise, for example, heating the polymer wrapped glass rod to form a glass and polymer rod preform, e.g., heating under vacuum at 290°C for 75 mins, followed by pressurization to atmosphere by adding N 2 gas to the oven and continued heating at 290°C for 5 more mins, as shown in Fig. 1.
• the method can further comprise, for example, drawing the glass and polymer rod preform to produce a drawn fiber, e.g., into continuous lengths of fiber using an optical fiber draw tower at about 445°C under Ar gas flow.
• the above drawn polymer-clad, glass core fiber can be, for example, a diameter of from 10 to 500 microns, e.g., 100 to 300 microns, as shown in Fig. 1.
• the method can further comprise any or all of the following steps, for example:
• step 2 making a fiber bundle preform
• thermoplastic film e.g., an outer layer of PE1 film.
• the heating can be, for example, baking at 170 to 190°C for at least 2 hrs and then stacking the fibers into a bundle of about 800 fibers (as shown in Fig. 2) and heat sealing this bundle with an outer layer of PE1 film by heating at 290°C for 90 mins under vacuum, followed by pressurization to atmosphere with N 2 and continued dwell at 290°C for 5 more mins.
• the method can further comprise, for example, drawing the fiber bundle preform into a first fine fiber (e.g., drawing the fiber bundle in an optical fiber draw tower at 420 to 440°C under Ar atmosphere), wherein continuous individual glass filaments in the composite have diameters, for example, from 2 to 10 microns, and the first fine microstructured fiber having an exterior diameter of about 100 to 300 microns (as shown in Fig. 2).
• a first fine fiber e.g., drawing the fiber bundle in an optical fiber draw tower at 420 to 440°C under Ar atmosphere
• continuous individual glass filaments in the composite have diameters, for example, from 2 to 10 microns
• the first fine microstructured fiber having an exterior diameter of about 100 to 300 microns (as shown in Fig. 2).
• the method can further comprise, for example, drawing the resulting first fine fiber into a second fiber bundle, heating and consolidating this second fiber bundle, then re-drawing this second fiber bundle into a second fine nanostructured fiber (e.g., at 410 to 420°C under Ar atmosphere) (i.e., step 3), and the second fine fiber having an exterior diameter of from about 10 to 150 microns.
• a second fine nanostructured fiber e.g., at 410 to 420°C under Ar atmosphere
• the disclosure provides a method of making a nanocomposite, comprising: contacting an oxide glass and a thermoplastic polymer at a temperature where each has a viscosity below 10 11 Poise, i.e., about 10 10 Pa-s, or even below about 10 8 Poise, to form the nano composite where the resulting organic, inorganic, or both, have a domain size having an average characteristic dimension along at least one direction, or at least two directions, that are less than 10 microns, less than 2 microns, less than 1 micro n, less than 0.5 microns, or even less than 0.1 microns.
• the disclosure provides an organic-inorganic composite comprising: an inorganic glass; and
• thermoplastic polymer a thermoplastic polymer
• thermoplastic surrounds the inorganic glass
• the inorganic glass comprises, for example, glass fibers, glass filaments, or mixtures thereof, having an average cross-section diameter less than 10 microns and a length to diameter (i.e., length:diameter; L:D) ratio greater than 100: 1, or an L:D even greater than about 1000:1.
• the inorganic glass and the thermoplastic polymer can have, individually or in combination, for example, a Tg of of from 300 to 450°C such as less than or equal to 450°C, about 400°C, or about 350°C or below, including intermediate values and ranges.
• the final product composite can have a visible optical transmittance of from 20% to greater than 50%, for a 0.1 mm thick section, e.g., about 20% for a 0.1 mm or even a 1 mm thick section.
• inorganic glass filaments e.g., as measured by filament number, volume, or cross-sectional area
• the inorganic glass can have, for example, a volume fraction of greater than 70% of the entire composite, or greater than 70% of a sub-region within the composite, the sub-region being at least about 100 x 100 x 100 microns in size, and the sub- region comprising 100 or more distinct inorganic domains partly or substantially separated by organic material such as measured when inspected by SEM or TEM or like methods.
• the composite can have, for example, an average tensile breakage strength (stress) of greater than 100 MPa, or greater than 200 MPa such as from 100 to 300 MPa, including intermediate values and ranges.
• the inorganic glass can comprise at least one of: an oxide glass, a fluoride glass, an oxyfluoride glass, a phosphate glass, a zinc sulfophosphate glass, or a combination thereof
• the disclosure provides an organic-inorganic composite, comprising:
• an inorganic phase comprised of an oxide, fluoride, or oxyfluoride glass situated in a plurality of adjacent domains;
• thermoplastic polymer an organic phase comprised of a thermoplastic polymer
• organic phase substantially surrounds or bounds the plurality of adjacent domains of the inorganic phase.
• the combined inorganic phase and organic phase define the domain sizes of the inorganic material, and at least one average characteristic dimension (e.g., two dimensions) of the inorganic domains is less than about 1 micron, and both the inorganic phase and the organic phase have a glass transition temperature, softening temperature, or both below about 450 D .
• the composite can have a two-dimensional array structure that is substantially continuous along one axis (e.g., along a fiber axis), and having an average characteristic dimension of discontinuous domains that is below 1 micron substantially in two dimensions (e.g., along two geometrical axes).
• the average characteristic dimension of the discontinuous domains can be, for example, below about 0.8 microns.
• the average characteristic dimension of discontinuous domains can be, for example, below about 0.5 microns.
• the inorganic phase can include a phosphate-containing glass.
• the inorganic phase can be a glass that is substantially free of: arsenic, selenium, tellurium, lead, chlorine, or any and all mixtures thereof.
• the inorganic phase or inorganic glass can have a volume fraction greater than about 70% of the entire composite, or greater than 70% of a sub-region within the composite, the sub-region being at least 100 x 100 x 100 microns in size, and the sub- region comprising 100 or more distinct inorganic domains partly or substantially separated by organic material.
• the composite can have a visible optical transmittance greater than 20% for a 0.1 mm thick section.
• the composite can have the organic phase and inorganic phase having a glass transition, a softening temperature, or both, below about 350 C .
• the composite can have an average tensile breakage strength (stress) of from 100 MPa, or greater.
• the thermal forming is a scalable manufacturing process
• the thermal forming permits secondary forming into complex articles, for example, using molding, fusing, blowing, embossing, pulling, drawing, extruding, wrapping, weaving, knitting, or 3D printing accompanied with temperature to soften or fuse the initial composite into complex shapes, for example auto parts, bone replacements, smartphone housings, and like structures, and the initial composite can be, for example, a sheet, a fiber, or a pellet; and the inorganic packing fraction, which can exceed the theoretical limit of wet spherical particle processes is feasible, for example, providing an inorganic volume fraction greater than 70, 80, or 90%.
• the oxide glass can have a T g , for example, of from about 500°C to 400°C, or less.
• the disclosed organic-inorganic composite can have an inorganic fiber or an inorganic filament density, for example, of greater than 100 fibers or filaments, visible in the composite when viewed in an SEM, TEM, or optical microscope.
• the at least 100 fibers or filaments can be substantially aligned in parallel with one another and the group of at least 100 fibers or filaments can be separated from one another by less than 1 inorganic fiber diameter, or less than 0.5 inorganic fiber diameters.
• the average physical thickness of the polymer matrix separating all of the at least 100 fibers can be, for example, less than 1 or less than 0.5 inorganic fiber diameters between each pair, or at least 80% of the pairs, of the at least 100 fibers.
• the inorganic fibers can be in contact or nearly in contact with one another, but the linear contact zone when viewed in an SEM cross-section can be, for example, less than 10% of the total inorganic fiber circumference, so that the inorganic fibers are still substantially separated by the polymer matrix between them.
• the disclosed organic-inorganic composite can have at least some of the inorganic fibers or filaments having a diameter, for example, of from 10 nm to 5 microns, such as less than 3 microns, less than 1 micron, less than 500 nm, less than 300 nm, or less than 200 nm.
• the disclosed organic-inorganic composite can have an inorganic or glass component that can comprise, for example, of from 50 to 70% by volume of the overall composite.
• the disclosed organic-inorganic composite can have an inorganic component, a glass component, or both that is substantially free of arsenic, selenium, tellurium, lead, and chlorine.
• the disclosed organic-inorganic composite can have an oxide glass that contains, for example, phosphorous, zinc, sulfur, or mixtures thereof.
• the disclosed organic-inorganic composite can have composite fibers having an average tensile breakage strength (stress), for example, of from about 100 to about 300 MPa.
• the disclosed organic-inorganic composite can have one or more composite sub-regions comprising, for example, greater than about 70%, greater than about 80%, or even greater than about 90% by volume fraction inorganic material, and at least the inorganic material is transparent to visible light, and the one or more composite sub-regions can be defined by, for example:
• the fibers or filaments are substantially aligned in parallel and the average spacing (substantially filled with organic material) or separation between fibers is, for example, less than one fiber diameter, the inorganic fibers or filaments having a cross-sectional diameter, for example, of less than 10 microns;
• the disclosure provides a method for making the disclosed composite(s) where the organic and inorganic components are both thermally formable due to substantial amorphous, glassy, or thermoplastic character, and the organic and inorganic components are thermally formed in contact with one another at an identical or near-identical process set point temperature(s) in a single process chamber or apparatus (e.g., an optical fiber draw tower, a multi-component melting apparatus, or a multi-component extruder, a nozzle, a die, an orifice, or other fixed point where the organic and inorganic components are brought together in a controlled manner).
• a single process chamber or apparatus e.g., an optical fiber draw tower, a multi-component melting apparatus, or a multi-component extruder, a nozzle, a die, an orifice, or other fixed point where the organic and inorganic components are brought together in a controlled manner.
• the organic and inorganic components can both have a viscosity below about 10 11 Poise (i.e., 10 10 Pa-s), below about 10 8 Poise, or even below about 10 7 Poise, at the point when they are brought into contact at an elevated temperature (e.g., a temperature of from than 50°C to 150°C or more).
• an elevated temperature e.g., a temperature of from than 50°C to 150°C or more.
• the disclosure provides a low-Tg or low-softening-point glass, which is preferably an oxide glass, a fluoride glass, an oxyfluoride glass, a phosphate glass, or a zinc sulfophosphate (ZSP) glass.
• the glass is melted and formed into rods using, for example, a molding or extrusion process, and then is coated or wrapped with a thermoplastic polymer.
• the glass-polymer combination is heated above the Tg or softening temperature of both the glass and the polymer and drawn into a fiber.
• This first fiber is then stacked or bundled into an array of many fibers, bonded together, then stretched or drawn again into a composite containing inorganic fibers with an average cross-sectional dimension, for example, below 10 microns substantially surrounded by an organic matrix.
• the stacking and re-drawing is optionally repeated again to further reduce the domain sizes.
• the final resulting inorganic fiber cross-section diameters (as an average of all the fibers, or as a portion of the fibers of from 10 to 50% of the population or more) can be, for example, 1 micron, 0.5 micron, 0.2 microns, 0.1 micron, including intermediate values and ranges.
• the disclosure provides a low-melting-point zinc sulfophosphate ("ZSP") glass.
• ZSP zinc sulfophosphate
• the glass was prepared by melting suitable proportions of sources or precursors for: zinc oxide, lithium phosphate, zinc pyrophosphate, potassium monophosphate, sodium hexametaphosphate, calcium carbonate, strontium carbonate, aluminum
• Fig. 1 shows images of process steps leading to a fiber draw step 1.
• Middle ZSP glass after cladding and vacuum heat sealing with a
• polyetherimide (PEl) polymer polyetherimide
• Top right PEl clad ZSP glass being drawn from a rod into a fiber, showing the thermal co-processing of both polymer and glass materials.
• Fig. 2 shows images of process steps leading to fiber draw step 2.
• step 1 Bundle of drawn fibers from the end of "step 1" (shown in Fig. 1), each fiber having a diameter of about 300 microns, are bundled into a new fiber "preform" having about a 12 mm diameter, and heat sealed with a secondary polymer cladding (PEl) layer.
• This preform was again drawn into the step 2 fibers shown macroscopically as a spool of fiber in the left-middle image, and microscopically in the SEM cross-section in the middle and right images.
• Step 2 (aka.: stage 2) fibers having a total diameter of about 100 to 300 microns have individual glass fiber or filament domain sizes, for example, of from about 2 to 10 microns.
• Fig. 3 shows SEM cross-section images of representative fibers resulting from fiber draw step 3.
• PEl polymer cladding
• This preform was drawn again into the step 3 fibers having a diameter of from about 200 to 500 microns.
• the fiber draw was somewhat non-uniform in this experiment, leading to varying sizes of composite domains and individual glass filaments. Individual glass fiber / filaments have diameters of from about 300 nm to about 1.5 microns in these images.
• Fig. 4 shows an SEM cross-section image of some of the smallest individual fiber/filaments within the composite matrix resulting from fiber draw "step 3". Individual glass filaments were measured as having a diameter as small as about 150 nm, and having filament diameters well below about 100 nm as seen in bottom left corner of the image. This image demonstrates the feasibility of creating unexpectedly small sulphophosphate glass fibers or filaments embedded in a polymeric matrix using thermal processing where both the discontinuous glass phase and the continuous polymer phase are above their respective softening points. The structural integrity of the nanofibers and of the glass / polymer composite is maintained throughout the thermal processing and SEM sample preparation.
• PE1 Polyetherimide
• Ultem® brand name Ultem®
• step 2 preform was then drawn into extended lengths (10's of meters) of continuous fiber with a polymer-glass composite structure as shown in the left-middle, middle, and right images and SEM cross-sections in Fig. 2, with continuous individual glass filaments in the composite having diameters from about 2 to 10 microns, and total fiber diameters of about 100 to 300 microns.
• step 2 fibers were drawn in an optical fiber draw tower at 420 to 440°C under Ar atmosphere.
• step 2 fibers were then bundled again to make a step 3 preform using the preceding processes, and drawn into a step 3 fiber at 410 to 420°C under Ar atmosphere. It was difficult to obtain long lengths of uniform fiber. Nevertheless short lengths of fiber (e.g., 1 to 10 cm in length) were obtained having individual glass domain sizes in the composite as small as 100 nm or less as shown in Fig. 3.
• the drawn fibers can have a tendency to shrink upon re-heating due to frozen chain alignment of the polymeric domains (aka. : 'shape memory' effect).
• Fiber shrinkage in excess of 80% was attained for step 3 fibers upon reheating to 350°C after drawing. While this could be useful for applications where shape memory is needed, in the present stack-and-redraw process this shrinkage effect led to nonuniform fiber drawing, particularly in step 3.
• a thermal relaxation treatment such as slow cooling or annealing, can be used to reduce or even eliminate the tendency of the drawn fibers to shrink, allowing them to retain uniform fiber shapes upon re-heating after they are drawn.
• annealing of the step 2 or step 3 fibers at a temperature such as 280°C, which is above the Tg of the polymer (for PE1, about 210°C) and below the Tg of the glass (for ZSP, about 310°C) for 1 to 10 hrs can reduce the resultant shrinkage by more than 50% upon later heating to 350°C.
• the shrinkage upon heating to temperatures higher than of from 10° to 40°C above the highest Tg component of the composite can be reduced to, for example, less than 20% to less than 1% of the original fiber length (i.e., essentially zero shrinkage).
• Shrinkage can also be tailored to a desired level or reduced using an in-line heating process during the fiber draw.
• Preliminary average tensile failure stress data on drawn composite fibers were measured as follows: Fibers were clamped and tested in tension using an Instron tensile loading apparatus using known methods. The breakage load was recorded and divided by the cross-sectional area of the fiber to establish an average breakage strength / stress level.
• the single fiber has a diameter of about 300 micron and an average tensile breakage strength (stress) of: 133 +/- 32 MPa.
• the composite fiber has a diameter of about 300 microns with 2 to 10 micron diameter glass sub-fiber / filament domains and an average tensile breakage strength (stress) of: 267 +/- 41 MPa.
• co-extrusion fiber spinning methods can be used to prepare the disclosed glass-polymer composite fibers.
• Multi-component co-extrusion and spinning of fibers can use multiple extruders, multiple materials, and a die system which generates complex fiber cross-sections such as described, for example, in US Patent
• bioactive, water soluble, or biodegradable glasses in combination with biodegradable or bioresorbable polymers can be selected for making the composite structure.
• These composite structures can be used, for example, as bandages, wound healing, tissue bonding, tissue growth promotion, biomedical implants, bone sutures, and like applications.
• silanes, block polymers, surface-active additives, or other coupling agents or surface treatments can be used to promote or tailor the adhesion between the organic and inorganic domains.
• the disclosure provides an organic-inorganic composite having discontinuous domains substantially along: two dimensions or two axes, for example, a fiber bundle, a honeycomb structure, a fiber, and like structures.
• a distinctive feature of the composite is that at least one average characteristic domain size along at least one dimension or axis can be, for example, 1 micron, 0.8 micron, 0.5 micron, 0.3 micron, or 0.1 micron, including intermediate values and ranges.
• Another distinctive feature of the disclosed composite is that both the organic and inorganic phases have a glass transition (Tg), a softening temperature, or both, of from 450D, of from 350D, of from 300D, or less than 300D, including intermediate values and ranges.
• Tg glass transition
• Another distinctive feature of the disclosed composite is that it remains thermally deformable.
• the inorganic phase may comprise an oxide, fluoride, or oxyfluoride glass. Still another distinctive feature of the composite is that the inorganic phase, the entire composite, or both, can have an optical transmittance greater than about 20% for a 0.1 mm thick or even a 1 mm thick section.
• a glass transition temperature (Tg) for both the organic and inorganic phase can be measured using known methods such as differential thermal analysis (DTA), differential scanning calorimetry (DSC), thermomechanical analysis (TMA), or dynamic mechanical analysis (DMA). Separate signals can typically be resolved in these tests for the organic and inorganic phases or components. In some instances, it is desirable to separate the signals from the organic and inorganic components using micromechanical approaches such as indentation, or by physically separating the organic and inorganic components, either by mechanical separation or by selective chemical etching and dissolution of one component.
• Softening temperature can be defined using various known test methods, such as the dilatometric softening test, Vicat softening test (ASTM D-1525), and heat deflection test (ASTM-D648).
• the disclosed composites can be used in a variety of applications, for example, water or oxygen vapor barriers, glass-reinforced polymer composites, molded parts such as automotive parts, textiles, fabrics, aerospace composite materials, rotors and turbines, optically transparent or translucent composite articles having high strength and toughness, cabling reinforcements such as optical fiber cabling reinforcements, architectural materials, structural materials, personal protective equipment, safety shields, biomedical implants, sutures, and like applications.
• Glass rods - ZSP glass rods Representative glass oxide compositions are known, see, for example, US 6268425, to Frayer (Glass K), and especially US 5328874, to Beall (Glass 6), and as listed in Table 1 (in mol%). These glass compositions were selected for their low Tg and softening temperatures and their relatively high mechanical strength, and chemical and moisture durability.
• Table 1 Representative glass oxide compositions.
• Table 2 lists a nominal composition that was targeted and actually realized for ZSP glass (in wt.%). [00102] Table 2. ZSP glass composition (wt.%).
• Table 3 lists batch materials in actual amounts used to prepare the disclosed oxide glass rods.
• PEI coated ZSP rod composite preforms Polyetherimide (“PEl”) films (brand name Ultem®) of 0.25 mm thickness were cleaned with isopropyl alcohol and baked in a vacuum oven at 190 °C for 2.5 hrs. These films were then wrapped onto the ZSP glass rods, held in place with PTFE tape, and heat sealed to the glass rods by heating under vacuum at 290°C for 75 mins, followed by pressurization to atmosphere by adding N 2 gas to the oven and continued heating at 290°C for 5 more mins.
• PEl Polyetherimide
• Method of making bundled fiber preforms The drawn fibers of Example 3 were processed into a "step 2" preform by baking at 170 to 190°C for at least 2 hrs and then stacking the fibers into a bundle of about 800 fibers (as shown in Fig. 2) and heat sealing this bundle with an outer layer of PEI film by heating at 290°C for 90 mins under vacuum, followed by pressurization to atmosphere with N2 and continued dwell at 290°C for 5 more mins.
• step 2 Method of making drawn bundled fibers
• This "step 2" preform of Example 4 was drawn into extended lengths (10's of meters) of continuous fiber with a polymer-glass composite structure as shown in the macroscopic pictures and in the SEM cross-sections in Fig. 3, with continuous individual glass filaments in the composite having diameters from about 2 to 10 microns, and total composite fiber diameters of about 100 to 300 microns.
• These step 2 fibers were drawn in an optical fiber draw tower at 420 to 440°C under Ar atmosphere.

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